Zhang Lin, Zhao Yaqi, Liu Chong, Pu Min, Lei Ming, Cao Zexing
State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 360015, China.
State Key Laboratory of Chemical Resource Engineering, Institute of Computational Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
Inorg Chem. 2022 Apr 11;61(14):5616-5625. doi: 10.1021/acs.inorgchem.2c00285. Epub 2022 Mar 31.
The conversion of carbon dioxide to fuels, polymers, and chemicals is an attractive strategy for the synthesis of high-value-added products and energy-storage materials. Herein, the density functional theory method was employed to investigate the reaction mechanism of CO hydroboration catalyzed by manganese pincer complex, [Mn(PhPCHSiMe)NH(CO)Br]. The carbonyl association and carbonyl dissociation mechanisms were investigated, and the calculated results showed that the carbonyl association mechanism is more favorable with an energetic span of 27.0 kcal/mol. Meanwhile, the solvent effect of the reaction was explored, indicating that the solvents could reduce the catalytic activity of the catalyst, which was consistent with the experimental results. In addition, the X ligand effect (X = CO, Br, H, PH) on the catalytic activity of the manganese complex was explored, indicating that the anionic complexes [Mn - Br] and [Mn - H] have higher catalytic activity. This may not only shed light on the fixation and conversion of CO catalyzed by earth-abundant transition-metal complexes but also provide theoretical insights to design new transition-metal catalysts.
将二氧化碳转化为燃料、聚合物和化学品是合成高附加值产品和储能材料的一种有吸引力的策略。在此，采用密度泛函理论方法研究了锰钳形配合物[Mn(PhPCHSiMe)NH(CO)Br]催化CO硼氢化反应的机理。研究了羰基缔合和羰基解离机理，计算结果表明羰基缔合机理更有利，能量跨度为27.0 kcal/mol。同时，探讨了反应的溶剂效应，表明溶剂会降低催化剂的催化活性，这与实验结果一致。此外，还探讨了X配体效应（X = CO、Br、H、PH）对锰配合物催化活性的影响，表明阴离子配合物[Mn - Br]和[Mn - H]具有较高的催化活性。这不仅可以为地球丰富的过渡金属配合物催化CO的固定和转化提供线索，还可以为设计新型过渡金属催化剂提供理论见解。
